Method for preparing an olefin polymerization feed stock



Patented on. 2, 1951 METHOD FOR PREPARING an oLmuN l POLYMERIZATION map srocx Raymond L. Heinrich, Baytown, m. mesne assignments, to Standard "s gna by Oil Development Company, Elizabeth, N. 1., a corporation of Delaware No Drawing. Application June 23, 1948. Serial No. 34,832

6 Claims. (01. 260-683.!)

The present invention is directed to an improved method i'or polymerizing oleflns in the presence of a Friedel-Crafts catalyst. More particularly, the invention has to do with the preparation of a feed stock for catalytic conversion operations. In its more specific aspects, the invention is concerned with the preparation of a feed stock for catalytic conversion operations from naphthas containing oleflns and oxygenated organic compounds.

Processes in which hydrocarbons are subjected to oxidation result in products including oxygenated organic compounds and low molecular weight hydrocarbons. The oxygenated compounds usually include the ketones, organic acids, aldehydes, esters, and the like, while the hydrocarbons produced from such oxidation reactions may include the olefins, both the monoand diolefin, paraflinic and naphthenic hydrocarbons, and possibly others. This mixture of oxygenated organic compounds and hydrocarbons, while a veritable storehouse of valuable materials in itself, is not particularly useful until the materials are separated according to type. For example, the oxygenated organic compounds of the type mentioned in admixture with each other or with the hydrocarbons are not particularly useful, I

but taken alone are quite valuable. Similarly, the oleflnic hydrocarbons in admixture with the other hydrocarbons and with the oxygenated organic compounds are not as valuable as the oleflnic hydrocarbon alone or simply in admixture with other hydrocarbons.

- The reaction of carbon monoxide and hydrogen over certain catalytic material in the so-called Fischer-Tropsch synthesis likewise produces a reaction product including hydrocarbons and oxygenated organic compounds of the type mentioned. The reaction product of carbon monoxide and hydrogen produced in the presence of when catalyst contains oleflns, paraflins, aromatics besides oxygenated organic compounds such as those found in the oxidation reaction mentioned above. The resolution of a mixture of hydrocarbons and oxygenated compounds into component parts has presented the industry with a serious separation problem. It is important to obtain the oxygenated organic compounds separated irom the hydrocarbons since they are valuable chemical raw materials, and it is also important to obtain the hydrocarbons substantially free or the oxygenated organic compounds. When the oxygenated organic compounds are present in oleflnic hydrocarbons, the hydrocarbons are less valuable as feed stocks to catalytic conversion operations than when the oleflnic hydrocarbons are substantially free of the oxygenated compounds.

Numerous methods have been suggested in the prior art of treating oleflnic hydrocarbons containing oxygenated organic compounds. Many of the methods suggested are open to serious economic objections in view of the tedious steps necessary to remove the oxygenated organic compounds from the naphtha or because chemicals approaching in value the value of the oxygenated compounds are required to treat these naphthas containing oleflns and oxygenated compounds.

It is, therefore. the main object of the present invention to provide a process for treating naphthas containing oleflns and oxygenated organic compounds to make such naphthas suitable for use in catalytic conversion operations.

Another object of the present invention is to' provide an improved polymerization process in.

which oleflnic naphthas containing oxygenated organic compounds and contaminants are treated to cause removal of the contaminating materials as high boiling reaction products.

It has been found that by treating oleflnic naphthas containing oxygenated organic compounds with reactive sulfides such as illustrated by hydrogen sulfide higher boiling materials are formed which may be separated from the oleflnic naphtha by distillation. Following the distillation operation, the naphthas may be polymerized in the presence of a Friedel- Cratts catalyst.

Accordingly, the present invention may be described briefly as involving the treatment of an oleflnic naphtha containing oxygenated organic compounds with a reactive sulfide at a temperature in the range from about 40 to 250 F. and at a reaction time ranging upwardly from about 1 minute to about 6 hours under conditions to cause the formation of a reaction product including material boiling substantially above the boiling range of the. oleflnic naphtha undergoing treatment. Following the treatment with the reactive sulfide the naphtha may then be subjected to treatment with an alkaline solution to and bisulfldes may having lubricating oil characteristics. The polymer may be distilled to separate said lubricating oil fractions which then may be used in lubricating internal combustion engines and the like. i

The reactive sulfide employed in the practice of the present invention is preferably hydrogen sulfide, but other sulfides such as the alkali metal sulfides as illustrated by lithium, sodium, and potassium sulfides, bisuliides and polysulfldes y be usedly, the ammonium sulfides also be employed. The phosphorus sulfides such as exemplified by phosphorus pentasulflde, phosphorus hexasulflde, and phosphorus heptasulfide may also be used. Many other reactive sulfides of the type mentioned could also be mentioned as being suitable in the practice of my invention.

It is desirable to cause initiation of the reaction by including in the reactive sulfide, such as hydrogen sulfide, an acidic material such as illustrated by gaseous hydrogen chloride. While gaseous hydrogen chloride is preferred as the activating material, other acidic bodies such as the non-gaseous strong acids such as sulfuric acid, nitric acid, as well as. the other halogen acids as exemplified by hydrobromic, hydroiodic, and the like may be used. 7

The Friedel-Craits catalyst employed in the polymerization step of my invention will preferably be aluminum chloride but other Friedel- Crafts catalysts such as titanium tetrachloride, zirconium chloride, ferric chloride, aluminum bromide and many other well known Friedelm Craf ts catalysts may be used.

The invention will be further illustrated by 4 The specific conditions under which the polymerization was conducted, the amount of catalyst employed, and the yields and tests of the products are presented in the following table:

Table 1 Untreated 0v n to e tZid B1 0 V8! 8m Naphtha Treated Treated Naphtha Naphtha Polymerization Tem F. 100 100 100 Polymerization 'llm inns... 120 on e so AlCh Catalyst; Wt. Per Cent of Oleflns Char '14. 8 14. 0 14.0 Polymer Yield, Wt. Per Cent of Oleflns Charged 21.0 40.0 .48. 7 Polymer Yield, Wt. Per Cent 01 Untreated Naphtha l1. 5 18. 9 10. 1 Sludge, Wt. Per Cent of Olefins Charged 34, 8 40. 7 36, 0

Test: on Polymer Viscosity at 210 F., s. s. U as 4 so a Viscosity Tudor 84 84 It will be seen from the foregoing data that when polymerizing the untreated naphtha, the 96% overhead fraction, and a 70% "overhead fraction, from the treated naphtha comparative resuits were obtained which show that substantially greater yields of polymer are obtained from the treated naphtha than from the untreated naphtha. The data also show that the polymer produced from the treated naphtha has a high viscosity index. The viscosity and viscosity index of the untreated naphtha were not. determined,

but prior experience has shown that such un-' treated naphthas when polymerized result in substantially lower quality plfoduct.

Additional runs were then made ona naphtha obtained by distilling the product resulting from a synthesis reaction in which carbon monoxide and hydrogen were'reacted over an iron ,oxide catalyst under synthesis conditions to produce a I product including oxygenated organic compounds and hydrocarbons. This distilled naptha reference to the following example in which a naphtha boiling in the range between 100 and 450 F. was obtained from a synthesis process in which carbon monoxide and hydrogen were re acted over an iron oxide catalyst to produce a product. The product was distilled to recover a, fraction in the afore-mentioned boiling range. This fraction was then treated as follows: Hydrogen sulfide containing about 1 mol per cent of hydrogen chloride was passed rapidly into 1000 volumes of vigorously stirred naphtha for 4 hours at 75 F. and at atmospheric pressure. 60

The resulting product after this reaction time was caustic washed and distilled in the presence of steam to recover a fraction corresponding to 70% of the treated naphtha, a second fraction corresponding to '70 to 96% of the treated naph- 05' the, and a third fraction amounting to 4% of the treated naphtha which was a viscous, black material. Portions of the '70%'overhead fraction and the total 96% overhead fraction were polymerized in the presence of aluminum chloride at a temperature in the range between and 250 F. to obtain a high boiling, high molecular weight polymer havinglubricating Oil characteristics. This polymer was then tested to de-.

' termine its viscosity and viscosity index.

had a boiling range from 110 to 400 F. and was treated in one instance with an aqueous alkaline solution including sodium hydroxide and in another instance in accordance. with the present invention with hydrogen sulfide and then washed with a portion of "the same aqueous solution of sodium hydroxide. The sodium hydroxide solution was separated from the two naphthas and i they were then separately polymerized in the presence of aluminum chloride at a temperature in the range given before and under conditions to form a polymer and an aluminum chloride sludge. The aluminum chloride sludge was separated from the polymer and the yield of the two determined. The unreacted naphtha remainingfrom the first polymerization was then subjected to a second polymerization treatment under similar conditions to produce a polymer and aluminum chloride sludge. The yields of the two were determined and the product ofthe second polymerization was then subjected to tests after distilling into a lubricating oil fractionand a sublube oil fraction; v

The specific conditions of the first and second polymerizations including the amount of aluminum chloride employed per volume of charge, the reaction time and the temperatures are given in the following Table II. The table also presents the tests on the products of the first and second polymerizations and gives in detail the inspection characteristics of the product of the second polymerization.

emos:

Table II Raw Raw Naphtha, Naphtha, ll400 F., ll0-400 HIS Treated Caustic 6 rs., Washed Caustic Washed 1 1m Polymerization am 350 l4 l4 0 0 153-106 163-167 Product: of First Polymerization Bub-Lube, cc 267 250 Lube, volumes 32 46 Sludge, parts 30. 3 28. 8

Tats on Products of First Polymerization Second Polymerization (Sub-Lube From First Polymerization) I Ch e volume 267 A16? datalyst, parts 8 Reaction Time, Hours 6 Temperature, "F 163-170 Product: of Second Polymerization Sub-Lube, volumes. 102 157 Lube, volumes 42 65 Sludge, parts 0. 2 l1. 3

- Tests on Products of Second Polymerization Lube:

Vis., 100 F 548 438 Vis., 210 F... 63.7 58.2 V. I 87 87 Gravity, API 31.0 31. 7 Sub-Lube:

Bromine Number 7a 0 62. 6 graiirliltyt, API 54. 4 53. 0 llfit 154 154 P 668 58] 194 109 272 289 450 504 merized in the presence of aluminum chloride to produce a high molecular weight polymer and an aluminum chloride sludge. The conditions used in the treating and polymerization steps and analyses and tests of the materials before and after polymerization are given in Table III, following:

Table III 1x100 Vol. Per Ceutoii0Wt.Per 2x100 Vol. Per Cent Aqueous Centof 'NaOH: Con- 10 Wt. Per Cent tacted with 1118-- Aqueous H01 Mixture; NaOH; 1x100 Vol. Per Redlstilled Coat of 10 Wt. Pei-Cent NaOH: Redistilled Treated Napbtha: Oxygenated Compounds, Wt. Per Cent Functional Group: OH (Alcohols) 0.35 0.26 CHO (Aldehydes)-- 0.00 0.00 0001! (Acids 0.00 0.00

84. 7 88. 0 4.6 4.0 6. 6 6. l is 6. 7 6. 2 Trisubstituted Ethylene 1.8 2.8

Polymerization Data:

Treating Temp., F 150-162 160-162 Charge, Volumes. 100 IN A1011, Parts 6 6 Reaction Time, Hrs 6 6 Yield of Lube Polymers Vol./100 Vol. Naphtha Chg; 18. 5 Tests on ube Polymer:

s. at 210 F-.- 66.13 64.8;

It will be seen-from the foregoing data in Table II that substantially greater yields of products are produced in accordance with the present invention than when polymerizing the raw naphthas which had been merely treated with sodium hydroxide solution. For example, the amount of lubricating oil from the first and second polymerizations increased from 74 volumes to 111 volumes when proceeding in accordance with the present invention. Moreover, the product produced in the first polymerization in accordance with the present invention was of a higher quality than the quality of the product from the first polymerization of the naphtha which had been merely treated with sodium hydroxide as shown by viscosity index data.

Another set of runs were carried out on a. naphtha obtained by distilling the product resulting from a synthesis reaction in which carbon monoxide and hydrogen were reacted over an iron oxide catalyst under synthesis conditions to produce a product containing oxygenated organic compounds and hydrocarbons. This distilled naphtha had a boiling range from 140 to 400 F. and was separated into two portions. One portion was washed twice with 100 volume percent of 10 weight percent sodium hydroxide and distilled. The other portion was washed with caustic solution, contacted with hydrogen sulfide containing a trace of hydrogen chloride, washed again with caustic solution, and distilled. The two treated fractions were then separately polya]: EBI IS'HCI mixture bubbled through naphtha for one hour ot about It will be noted from the foregoing data that the content oi oxy organic compounds in the redistilled naphtha in both cases was substantially the same showing that the treatment of the naphtha with sodium hydroxide and with hydrogen sulfide-hydrogen chloride mixture did not effect a much greater removal of the materials but when employing a somewhat higher ratio 01.

aluminum chloride to treated naphtha as shown in Table III, a higher yield of lubricating polymer was obtained.

It has been mentioned that various active sulfides, of which specific examples have been given, may be used in my invention. It is also possible to employ naphtha fractions which contain active sulfides and to use these materials in producing feed stocks which are valuable in catalytic conversion operations. For example, an oxygen-containing olefinic naphtha may have added to it oleflnand sulfur-bearing fractions from petroleum refining operations. Such fractions: may include either liquids or' gases containing hydrogen sulfide or mercaptans and the like. Similarly, the alkali metal sulfides may be found in treating whatIwishtoclaimasnew andusei'ul and to secure by Letters Patent is: 1. A method for preparing a feed stock for a catalytic polymerization operation which comprises contacting a naphtha containing olefins and oxygenated organic compounds with hydrogen sulfide at a temperature in the'range between 40 and 250 F. for a time suiilcient to form a reaction product including material boiling'above the boiling range of the naphtha and unreacted material, subjecting said contacted naphtha to aseptiration treatment to separate therefrom said reaction product and recovering from said separation treatment a fraction suitable for use as a. feed stock in a catalytic polymerization operation.

2. A method in accordance with claim 1 in which the separation treatment is a distilling operation.

3. A method for preparing a feed stock for a catalytic polymerization operation which consists of contacting a naphtha boiling in the range between 110 and 450 F. and containing oleflns and oxygenated organic compounds. with hydrogen sulfide at a temperature in the range between 40" and 250 F. and for a time in the range between 1 minute and 6 hours to form a reaction product including material boiling abovethe boiling-range of the naphtha, distilling said contacted naphtha into a fraction boiling in the boiling range of said naphtha and a fraction boiling outside said boiling range of saidnaphtha and recovering said fraction boiling in the boiling range of said naphtha for use as a feed stock in a catalytic polymerization operation.

4. A method for producing a high molecular weight polymer boiling in the lubricating oil boiling range which comprises contacting a naphtha 8 fractions, one boiling in the boiling ran e of said feed naphtha and one boiling above the boiling range of said feed naphtha, subjecting said distilled fraction boiling in the boiling range of said feed naphtha to polymerization conditions including contact with a Friedel-Crafts catalyst under conditions to form a product including a high molecular weight polymer in the lubricating oil boiling range, and distilling said product to recover said polymer in said lubricating oil boiling range.

5. A method in accordance with claim 4 in which the Friedel-Crafts catalyst is aluminum chloride.

6. A method for preparing ,a high molecular weight polymer having lubricating oil characteroutside the range of said feed naphtha, contactin said first fraction with a Friedel-Crafts catalyst under polymerization conditions to form a product including a polymer in the lubricating oil boiling range and distillating said product to recover a fraction having lubricating oil characteristics.

RAYMOND L. HEINRICH.

REFERENCES crrEn The following references are of record in the flle of this patent:

UNITED STATES PATENTS Number Name Date 2,055,425 Caudri Sept. 22, 1936 2,059,495 Smeykal Nov. 3, 1936 2,075,295 Loder Mar; 30, 1937 2,165,372 Haag et al July 11, 1939 2,315,080 Reid Mar. 30, 1943 2,446,231 Johnson Aug. 3, 1948 2,494,371 Wadley Jan. 10, 1950 OTHER REFERENCES Richter's Organic Chemistry, vol, I, pages 23 1, 266 and 267 (1934). 

1. A METHOD FOR PREPARING A FEED STOCK FOR A CATALYTIC POLYMERIZATION OPERATION WHICH COMPRISES CONTACTING A NAPHTHA CONTAINING OLEFINS AND OXYGENATED ORGANIC COMPOUNDS WITH HYDROGEN SULFIDE AT A TEMPERATURE IN THE RANGE BETWEEN 40* AND 250* F. FOR A TIME SUFFICIENT TO FORM A REACTION PRODUCT INCLUDING MATERIAL BOILING ABOVE THE BOILING RANGE OF THE NAPHTHA AND UNREACTED MATERIAL, SUBJECTING SAID CONTACTED NAPHTHA TO A SEPARATION TREATMENT TO SEPARATE THEREFROM SAID REACTION PRODUCT AND RECOVERING FROM SAID SEPARATION TREATMENT A FRACTION SUITABLE FOR USE AS A FEED STOCK IN A CATALYTIC POLYMERIZATION OPERATION. 